EP0963979A1 - Verfahren zur Herstellung von 1,2,4-Triazolen ausgehend von Ketazinen - Google Patents

Verfahren zur Herstellung von 1,2,4-Triazolen ausgehend von Ketazinen Download PDF

Info

Publication number
EP0963979A1
EP0963979A1 EP99108294A EP99108294A EP0963979A1 EP 0963979 A1 EP0963979 A1 EP 0963979A1 EP 99108294 A EP99108294 A EP 99108294A EP 99108294 A EP99108294 A EP 99108294A EP 0963979 A1 EP0963979 A1 EP 0963979A1
Authority
EP
European Patent Office
Prior art keywords
ketazine
triazole
producing
cyclization
formamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99108294A
Other languages
English (en)
French (fr)
Other versions
EP0963979B1 (de
Inventor
Nobuhiro Mitsubishi Gas Chemical Cpy Inc. Nagata
Chiharu Mitsubishi Gas Chemical Company Nishizawa
Toshikiyo Mitsubishi Gas Chemical Cpy Inc. Kurai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Publication of EP0963979A1 publication Critical patent/EP0963979A1/de
Application granted granted Critical
Publication of EP0963979B1 publication Critical patent/EP0963979B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to a method of producing 1,2,4-triazole which is a useful compound having numerous applications such as a starting material for synthesizing agricultural chemicals.
  • the ketazine is an intermediate of industrial hydrazine production, and hydrazine is produced by hydrolysis of the ketazine. A substantial portion of energy required in the hydrazine production is consumed during the hydrolysis of the ketazine to result in increased cost of producing hydrazine. This in turn increases the production cost of 1,2,4-triazole.
  • an object of the present invention is to provide a method of producing 1,2,4-triazole with a low cost without reducing the yield thereof.
  • the inventors have extensively studied synthesis of 1,2,4-triazole using a ketazine as the starting material in place of hydrazine.
  • 1,2,4-triazole is easily synthesized by conducting the cyclization reaction while gradually adding a ketazine and water to formamide kept at a cyclization temperature, and distilling off ketone formed during the cyclization reaction.
  • the present invention provides a method of producing 1,2,4-triazole, comprising a step of subjecting a ketazine, water and formamide to cyclization reaction.
  • the ketazine referred to in the present invention is an aliphatic ketazine having a total carbon number of 3-13, such as a dialkyl ketazine, a cycloalkyl ketazine and a cycloalkanone azine.
  • Specific examples of the ketazine may include acetone azine, methyl ethyl ketazine, methyl isobutyl ketazine, cyclohexanone azine, etc.
  • acetone azine and methyl ethyl ketazine used in the industrial production of hydrazine are preferable because they are economical due to their easy availability and easy handling ability.
  • the ketazine and water simultaneously to formamide kept at a cyclization temperature under stirring.
  • the simultaneous addition of the ketazine and water may be accomplished by adding both as a mixture or individually at a time.
  • the amounts of formamide and water to be used are not specifically limited so long as they are used stoichiometrically or more with respect to the ketazine. In view of industrial economics, the upper limits of the amounts of formamide and water are preferred to be as small as possible.
  • the amount of formamide to be used is preferably 10 times or less, more preferably 5 times or less by mole based on the ketazine, and preferably 5 times or less, more preferably 3 times or less by mole for water based on the ketazine.
  • the cyclization temperature is 100-210°C, preferably 150-210°C.
  • the cyclization is generally conducted under ordinary pressure, it may be conducted under reduced pressure or increased pressure.
  • the rate of addition of the ketazine and water depends on the cyclization temperature, reacting weight, shape and size of a reaction apparatus, etc.
  • the temperature of the reaction mixture is needed to be kept within the above cyclization temperature range and ketone formed during the cyclization reaction should be distilled off. thereby shortening the residence time of the ketone in the reaction system.
  • the ketazine and water are preferably added to formamide over about 3 to 15 hours.
  • 1,2,4-triazole is easily synthesized from ketazine, water and formamide without using hydrazine. Since the energy-consuming step of hydrolyzing a ketazine into hydrazine inevitable in the conventional hydrazine production can be eliminated, the present invention provides an energy-saving overall method of producing 1,2,4-triazole.
  • ketone by-produced in the method of the invention is very volatile and easy to distill off as compared with by-products in the conventional method using hydrazine. This ensures a high yield and purity of 1,2,4-triazole without a purification step, and enhances the advantage of the present invention in energy consumption over the conventional methods.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP99108294A 1998-05-12 1999-04-28 Verfahren zur Herstellung von 1,2,4-Triazolen ausgehend von Ketazinen Expired - Lifetime EP0963979B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP12899798 1998-05-12
JP12899798 1998-05-12

Publications (2)

Publication Number Publication Date
EP0963979A1 true EP0963979A1 (de) 1999-12-15
EP0963979B1 EP0963979B1 (de) 2006-12-27

Family

ID=14998593

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99108294A Expired - Lifetime EP0963979B1 (de) 1998-05-12 1999-04-28 Verfahren zur Herstellung von 1,2,4-Triazolen ausgehend von Ketazinen

Country Status (3)

Country Link
US (1) US6002015A (de)
EP (1) EP0963979B1 (de)
DE (1) DE69934544T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946733A (zh) * 2017-04-26 2017-07-14 重庆丽澄环保科技有限公司 一种制备己二酸二酰肼的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104230830B (zh) * 2014-10-11 2016-03-30 重庆锦杉科技有限公司 三氮唑的合成方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267346A (en) * 1978-01-20 1981-05-12 Bayer Aktiengesellschaft Process for the preparation of 1,2,4-triazole
EP0030209A1 (de) * 1979-11-07 1981-06-10 Ciba-Geigy Ag Verfahren zur Herstellung von 1H-1,2,4-Triazol
JPS5695177A (en) * 1979-12-28 1981-08-01 Koei Chem Co Ltd Production of 1,2,4-triazole
US4283545A (en) * 1979-10-26 1981-08-11 Hoechst Aktiengesellschaft Process for the preparation of 1,2,4-triazole
US4323705A (en) * 1979-10-26 1982-04-06 Hoechst Aktiengesellschaft Process for the preparation of N,N'-diformylhydrazine
US4390704A (en) * 1980-07-07 1983-06-28 Chemie Linz Aktiengesellschaft Process for the preparation of 1,2,4-triazole
US4725421A (en) * 1975-09-10 1988-02-16 Atochem Process for the preparation of concentrated solutions of hydrazine hydrate
EP0758642A2 (de) * 1995-08-14 1997-02-19 Mitsubishi Gas Chemical Company, Inc. Verfahren zur Herstellung von Ketazinen und Hydrazinhydrat

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490539A (en) * 1982-06-22 1984-12-25 Nehezvegyipari Kutato Intezet Process for the preparation of 1,2,4-triazole

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4725421A (en) * 1975-09-10 1988-02-16 Atochem Process for the preparation of concentrated solutions of hydrazine hydrate
US4267346A (en) * 1978-01-20 1981-05-12 Bayer Aktiengesellschaft Process for the preparation of 1,2,4-triazole
US4283545A (en) * 1979-10-26 1981-08-11 Hoechst Aktiengesellschaft Process for the preparation of 1,2,4-triazole
US4323705A (en) * 1979-10-26 1982-04-06 Hoechst Aktiengesellschaft Process for the preparation of N,N'-diformylhydrazine
EP0030209A1 (de) * 1979-11-07 1981-06-10 Ciba-Geigy Ag Verfahren zur Herstellung von 1H-1,2,4-Triazol
JPS5695177A (en) * 1979-12-28 1981-08-01 Koei Chem Co Ltd Production of 1,2,4-triazole
US4390704A (en) * 1980-07-07 1983-06-28 Chemie Linz Aktiengesellschaft Process for the preparation of 1,2,4-triazole
EP0758642A2 (de) * 1995-08-14 1997-02-19 Mitsubishi Gas Chemical Company, Inc. Verfahren zur Herstellung von Ketazinen und Hydrazinhydrat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 005, no. 164 (C - 076) 21 October 1981 (1981-10-21) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106946733A (zh) * 2017-04-26 2017-07-14 重庆丽澄环保科技有限公司 一种制备己二酸二酰肼的方法

Also Published As

Publication number Publication date
EP0963979B1 (de) 2006-12-27
DE69934544T2 (de) 2007-04-26
DE69934544D1 (de) 2007-02-08
US6002015A (en) 1999-12-14

Similar Documents

Publication Publication Date Title
EP0413064A1 (de) Herstellung von 2-Phenyl-propan-1,3-diol und dessen Dicarbamat
CA1060044A (en) PROCESS FOR PREPARING .gamma.-AMINO-ACID AMIDE
US6002015A (en) Method of producing 1,2,4-triazole
US4230869A (en) Process for preparing 5-(4-hydroxyphenyl)hydantoin
CA1310017C (en) Process for the preparation of 2, 6-dichlorodiphenylamino-acetic acid derivatives
EP0877015B1 (de) Verfahren zur Herstellung von Cyclopropancarboxamid
EP0618200B1 (de) Verfahren zur Herstellung von Aminotriazin-Derivaten
EP0697402B1 (de) Verfahren zur Herstellung von Prosulfocarb
US4720553A (en) Method for synthesizing N-aminophthalimide
US4283344A (en) Process for producing 1,1,3,3-tetrafluoro-1,3-dihydro-isobenzofuran
JP2926375B2 (ja) ヒドロキシカルボン酸エステルの製造法
EP0204286B1 (de) Herstellungsverfahren von Estern der Trans-alpha-benzoylacrylsäure
KR890003598B1 (ko) 시아노히드린의 제조방법
AU542171B2 (en) Thiochloroformate from phosgene and mercaptan
US4582941A (en) Process for producing squaric acid
JP3257779B2 (ja) タートラニル酸類の製造法
JP3214923B2 (ja) 第３級ヒドロペルオキシドの製造方法
US4211704A (en) Method for producing 2,3,3-trimethylindolenine
JP2000034283A (ja) １，２，４―トリアゾ―ルの製造方法
JPS58120507A (ja) ヒドラジンの連続的製造方法
RU2039732C1 (ru) Способ получения метилендиацетата
JPS6053021B2 (ja) ヒダントインの製造法
JP2001247509A (ja) ２，３，５，６−テトラクロロ−１，４−ベンゼンジカルボン酸の製造方法
JPS61140561A (ja) アジリジン−２−ニトリルないしアジリジン−２−カルボン酸アミドの製造法
JP3820557B2 (ja) ５−アミノ−２−ニトロフェノールの製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20000522

AKX Designation fees paid

Free format text: DE FR GB

17Q First examination report despatched

Effective date: 20040226

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69934544

Country of ref document: DE

Date of ref document: 20070208

Kind code of ref document: P

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070619

Year of fee payment: 9

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070426

Year of fee payment: 9

26N No opposition filed

Effective date: 20070928

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070419

Year of fee payment: 9

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080428